N-cycloalkylidene-n&#39;-cycloalkyl-1-enyl-thioureas and method of preparation



United States Patent N -CYCL()ALKYLIDENE N CYCLOALKYL-l- ENYL-THIOUREAS AND METHOD OF PREP- ARATION Charanjit Rai, Crystal Lake, 111., assignor, by mesne assignments, to Union Oil Company of California, Los Angeles, Calif., a corporation of California No Drawing. Filed July 17, 1963, Ser. No. 295,794 13 Claims. (Cl. 260-552) it IC---NH2 In accordance with this invention I have found that the reaction of cyclic ketones with thiourea or substituted thioureas gives different products and the reaction may be represented by the equations:

Equation 1 CH2 R1 s 2R 0:0 NCNH H/ (or Base) cm s H R H R laminae in either an acid or base catalyzed reaction and also where .CII

is substituted or unsubstituted cyclohexanone, the following reaction predominates:

R in Equation 1 is a divalent radical of the group consisting of unsubstituted methylene chains of the formula -(CH wherein n is 2 to 9, substituted methylene chains of the formula 3,320,311 Patented May 16, 1967 "ice wherein Y is a substituent of the group consisting of hydrogen, methyl, ethyl, propyl, butyl radicals, chlorine and fluorine. Also the beta carbon atom in the cyclic ketone may have one hydrogen atom thereof substituted with a Y substituent. Where two or more Y substituents are present they may be the same or different members of the foregoing group. These same considerations apply to the -CH units of cyclohexanone in Equation 2.

R of the thiourea compound can be hydrogen or any C to C hydrocarbon substituent, and preferably is a substituent of the group consisting of hydrogen, C to C straight-chain or branched-chain aliphatic radicals such as methyl, propyl, isobutyl and t-buty1, aryl radicals having 6 to 18 cyclic carbon atoms, such as phenyl, naphthyl and anthryl, the corresponding C to C -alkyl substituted aryl radicals where the alkyl substituents are as heretofore defined and said aryl radicals can contain from 1 to 5 such substituents for phenyl radical, 1 to 7 such substituents for the naphthyl radical and 1 to 9 such substituents for the anthryl radical, for example the corresponding aralkyl radicals such as phenylmethyl, phenylethyl, naphthylmethyl and phenylbutyl and C to C cycloaliphatic radicals such as cyclopropyl, cyclobutyl and spiropentyl which are attached thereto as monovalent radicals or which are joined to adjacent carbon atoms to form a double ring system and the like.

Accordingly it is an object of this invention to provide a novel method of condensing cyclic ketones and thioureas and to prepare novel compounds having the formulae:

(I) OH S H R 2 R tanning and (II) R wherein R and R are as previously defined to include the substituent Y on the methylene groups in each of the formulae.

Another object of this invention is to provide as new compounds N-cycloalkylidene-N-cycloalkyl-1-enyl thioureas (Formula I) and the method of preparing such compounds. Another object of this invention is to provide as new compounds 2-cyc1oalkyll-enyl cycloalkyl-lenyl-thioureas (Formula II) and the method of preparing such compounds.

A further object of this invention is to provide a N-cyclohexylidene-N'-cyclohexyl-l-enyl thiourea as a new composition of matter and the method of preparation thereof.

Still another object of this invention is to provide derivatives of the compounds herein disclosed.

And another object is to provide 2-cyclohex-1-enyl-cyclohex-l-enyl thiourea and the method of preparation thereof.

These and other objects of this invention will be described or become apparent as the specification proceeds.

The base-catalyzed condensation of cyclohexanone and thiourea has been found to produce two isomeric products having the emperical formula, C H N S said isomeric mixture predominating in an isomer I (yellowish in color) (I) H s -N-cyclhexy1idene N-cychex-1-enyl thiourea melting at about 218 C. and containing a small amount of an isomer II (2-cyclohex-1 enylcyclohex1-eny1-thiourea (colorless) melting at 266 C. The isomer I on refluxing with hydrochloric acid gave isomer II. The higher melting isomer II was also formed by the acid-catalyzed condensation of thiourea with cyclohexanone in 72% yield.

In the presence of acids cyclohexanone is known to undergo self condensation to give 2-cyclohexylidene-cyclohexanone. When thiourea was condensed with 2-cyclo hexylidene-cyclohexanone, 30 prepared, in the presence of hydrochloric acid, the isomer II resulted. The melting point of a mixture of the latter product with the previously prepared isomer II, remained undepressed and the infrared spectra of the two compounds were identical.

The similar base-catalyzed reactions of other cyclic ketones with thiourea gave products having infrared and ultraviolet spectra similar to the low melting isomer I, whereas the acid-catalyzed reactions of these ketones resulted in products similar to the high melting isomer II. However, the condensation of cycloheptanone and thiourea, whether catalyzed by a base 'or an acid, gave the same product, the low melting isomer, C H N S. When the condensation of 2-cyclohexylidene-cyclohexanone was carried out in the presence of a base, such as triethanolamine, the same product, C H N S, the higher melting isomer II, was isolated in somewhat lower yields.

Cyclohexanone exists in a keto and an enol form, the latter being present up to 2 10- percent in the liquid state. It is suggested that the base-catalyzed reaction of cyclohexanone and thiourea proceeds through the enolic form and does not involve the intermediate of the acidcatalyzed reaction, 2 cyclohexylidene cyclohexanone. Two structures (I and III) (Ncyelohexylidene N -eyc1ohex-1-euyl thiolu rea) (III) double bond. The infrared spectrum indicated the presence of NH stretching bands around 3225 cm. and 1546 CHI-"1, a CH stretching and bending band at 3050 cm. a C -"N band at 1585 CII'L'I and C=S band at 1400 cm.- and 1365 cmr The C==C band is generally weak and shows absorption at 1620 cmf A very weak band at 1685 cm.- may be due to C=C. The ultraviolet spectrum of the compound shows absorption at 297 and 357 mg, and resembles the absorption spectrum of thioketones thereby supporting the presence of a C=S group. All this data points to structure I for the lowermelting isomer C H N S.

The condensations of 2-methylcyclohexanone, 3-methylcyclohexanone, and 4-methylcyclohexanone with thiourea were also studied in a basic medium. The resulting compounds were formed in low yields and their infrared spectra were similar to that of I. The ultraviolet spectra of these compounds gave absorption peaks, with A at about 358 and 299 mu as compared with that of compound I having kmax, at 357, and 297 mu. Their structures may be represented by I with the proper substituents on cyclohe'xyl and cyclohex-l-enyl rings. These compounds are shown in Tables I, III and V.

The base-catalyzed cycloheptanone and thiourea condensation resulted in the product, C H N S, which could also be prepared by the acid-catalyzed reaction in low yields. Cyclopentanone and thiourea condensation gave a viscous oil which did not crystallize and was not studied further.

The acid-catalyzed condensation product of thiourea with cyclohexanone or 2-cyclohexylidene-cyclohexanone may be represented by the following structures:

(2-cyclol1e-x-l-enyl-cyclohex-l-enyl thiourea) ii HiNC-N= D C) ('2-cyclol1exy-1idene-cyclohexylidene thiourea) The formation of a tetrabromide, C H N SBr indicated the presence of two double bonds in the molecule. The ultraviolet spectrum with A values of 275 and 256 my. supports structure II. This was confirmed further by the infrared spectrum of the compound. The absorptions at 3350, 3205 and 1554 cm. are due to N--H stretching and bending bands; the bands at 3075 cm? and 3060 cm. are probably due to the CH stretching vibration and will only result from structure II. A strong band at 1690 emfmay be due to the absorption resulting from the conjugated double bonds of the molecule. Generally, conjugation in aliphatic compounds lowers the absorption frequency. The absorption peak in the region 161804670 cm? to RR C CHR and 1655-1645 cm:- peak is assigned to RR C==OH and peaks at 1690 cm.- and 1645 are assigned to the bands of polymerized 2,3- dimethylbutadiene to the two types of double bonds. The absorption at 1365 cm. may be assigned to C=S The ultraviolet spectrum of the N-phenylthiourea derivative showed a x at 264 mu.

The condensation of 2-methylcyclohexanone 3-methylcyclohexanone, and 4-methylcyclohexanone with thiourea was also studied in acidic medium. The new compounds thus prepared are listed in Tables II, IV and VI. 3-methylcyclohexanone and 4-methylcyclohexanone reacted with thiourea to give crystalline products but Z-methylcyclohexanone gave an oily product which was not investigated further. The infrared absorptions and ultraviolet absorptions indicated that the structures of the products are similar to that of compound II.

' Structures I and II were further confirmed by NMR A small portion, 1.5 g., of the crude product did not dissolve in warm ethanol. It was colorless and melted at 260262. After recrystallization from p-dioxane the melting point was 266. This product was characterized as Z-cyclohex-l-enyl cyclohex-l-enyl thiourea, isomer II.

The compounds described in Table I were prepared by the general procedure described above for the preparation of N-cyclohexylidene-N'-cyclohex-1-ei1yl thiourea.

TABLE I.-BASE CATALYZED CONDENSAIION PRODUCTS OF THIOUREA WITH CYCLIC KE'IONES Thioura Type Ketone Reactant H V Condensation Product. Calcd. Found Reactam M.p., 0. Yield Formula C H N S C H N S percent ETgNJli-NH: Cyclohexanone. 218 48 C13H2oN2S 66.10 8. 48 11.86 13. 56 66. 05 8.95 ll. 05 13. 35

S CaH NHi JNHz d0 210 15 C13H20N2S 06.10 8. 48 11. 86 13. 5G 66. 9.00 11. 13. 50

S CH =C]INH-( JNH2 lO 220 10. 2 C13H20N2S-- 6G. 10 8. 48 11. 86 13. 56 66.50 9. 20 11. 10 13. 20

s e v H2NH7-NH 21;;(tEQyl-cyclohex- 203-204 9. 56 CisH24N2S 68.18 9.09 10. 61 12. 12 67. 8O 9. 9D 10.20 12.

S HzNL-NH: fi lggggl-cyclohex- 225-226 12. 2 CisHnN2S 68. 18 9. 09 10. 61 12. 12 08. 30 9. G0 10. 25 11.85

S H2N( J-NHQ tigefigl-cyclohex- 246-248 15. 0 Ci5H24N2S 68. 18 9. 09 10. 61 12. 12 68. 20 9. S0 10. 10 11. 90

S HzNii-NH: Cycloheptanone 227-228 14. 0 C15II24N2S 68.18 0. 09 10. 01 12. 12 68.10 9. 10. 20 12. 2

spectra of the two isomers. The presence of vinylic proton peak at 5.5 p.p.m..and two broad bands consisting of several peaks at about 1.62 and 1.82 ppm. in the NMR spectrum of isomer I excluded structure III for the compound. The ratio of the -CH proton peak area to the -CH proton peak area was 18 and could only arise from structure I having only one vinylic proton. The presence of a vinylic proton peak at 5.35 ppm. and two methylene proton peaks (one due to the hydrogens of the methylene groups unshielded by the diene system at 2.0 ppm. and the other due to the shielded hydrogen) at 1.6 ppm. in the NMR spectrum of compound II confirmed structure II for the isomer instead of structure IV. The NMR spectra were taken in chloroform.

In order to demonstrate the invention the following examples are given which confirm the operability of the process and the structures of the products.

All the melting points reported here are corrected and were determined in a capillary tube in the usual manner.

EXAMPLE I Preparation of N-cyclohexylidene N'-cycl0hexyl-Z-enyl thiourea (isomer I Thiourea (19 g., 0.25 mole), cyclohexanone (50 g., 0.51 mole) and triethanolamine (5 g.) were mixed in a heated flask and refluxed for two hours. The reaction mixture was cooled and dissolved in warm aqueous ethanol (150 ml.) and allowed to cool whereupon a yellow precipitate appeared. The precipitate was filtered oil and dried giving 26.4 g. of crude product, melting at 214- 216. On recrystallization from ethanol, the melting point of I increased to 218-219".

EXAMPLE II lsomeriztaion of N-cyclohexylidene, N'-cycI0hex-1-enyl thiourea with hydrochloric acid to 2-cycl0hexJ-enyl cyclohex-l-enyl thl'ourea A mixture of N cyclohexylidene-N'-cyclohex-1-enyl thiourea (2.0 g.) and 20% hydrochloric acid (20 ml.) was refluxed for 1 /2 hours. The product was cooled and filtered. The melting point of the residue was 256-58. On recrystallization from p-dioxane the melting point was 262264. The mixed melting point of this product with the isomer II was undepressed, and the infrared spectrum of the two compounds was identical.

EXAMPLE III Z-cyclohexylidene-cyclolzexarzone 2-cyclohexylidene-cyclohexanone, B.P. 154-155 at 19 I111'I1JZD20 1.5070 was prepared in 71% yield by the method of Gault et al., Bull. Soc. Chim., France 12,952 (1945).

EXAMPLE IV Preparation 0 2-cycl0hex-I-eny1 cyclolzex-Lenyl thiourea from cyclolzexanolze TABLE II.ACID-CATALYZED CONDENSATION PRODUCTS OF THIOUREA WITH CYCLIG KETONES Condensation Product Calcd. Found R Ketone Reaetant M.P., Yield Formula C H N S C H N S percent H Cyclohexanone 266 72. 1 C1aHzoNzS.... 66. 10 8. 48 11.86 13. 56 66. 10 8.90 11. 65 13. 35 PhenyL do 160-61 3 8 CIQHHN 73. 7. 75 8. 95 10. 25 73. 7. 80 9. 00 10. 10 H 4-Methyl-eyclohexan0ne. 194-195 18. 2 24N2S.... 68. 18 9. 09 10.61 12. 12 68. 9. 30 10. 45 12.05 H 3-Methyl-cyclohexanone 186-87 16. 4 C15H24N2S 68. 18 9. 09 10.61 12. 12 68. 05 9. 35 10. 50 12. 10 Cycloheptanone* 227-23 15. 7 C15H21NQS. 68. 18 9. 09 10. 61 12. 12 68. 20 9. 35 10. 35 12. 10 H 2-Cyclohexylidene-Cyclohex- 266 82. 2 C1aI-I2oN:S 66. 10 8. 48 11.86 13. 56 66. 10 8. 75 11. 65 13. 50

anone.

The structure of the product from eycloheptanone is similar to the base catalyzed reaction products.

EXAMPLE V Preparation of 2-cyclohex-1-enyl cycl0hex-1 -enyl thiourea from 2-cycl0hexylidene-c'yclohexanone of Example III Method 1.-A mixture of thiourea (15.2 g., 9.2 mole), 2-cyclohexylidene-cyclohexanone (35.6 g., 0.2 mole) and concentrated hydrochloric acid (10 cc.) was refluxed for one hour, and a colorless crystalline solid precipitated. The solid was recovered "by filtration and washed with ethanol. The yield was 34.1 g. (72% The mixed melting point of this compound with compound II was undepressed and the infrared spectra of the two compounds were identical.

Method 2.A mixture of thiourea (15.2 g., 0.2 mole), 2 cyclohexylidene-cyclohexanone (35.0 g., 0.2 mole) and triethanolamine (5 cc.) was refluxed for one hour when a slightly yellowish solid product separated. The latter was filtered and washed with ethanol; the yield was 29.3 g. (61.5%). The mixed melting point with compound II was undepressed and the infrared spectra of the two substances were identical.

EXAMPLE VI The N-phenyl-N'-(2 cyclohex-l-enyl cyclohex-l-enyl) thiourea was also prepared according to the method 1 of Example V.

EXAMPLE VII Preparation of N-cycloheptylidene N'-cycl0hept- I-enyl thiourea Thiourea (7.6 g., 0.1 mole) cycloheptanone (22.4 g., 0.2 mole) and triethanolarnine (5 cc.) Were refluxed together for two hours. The viscous product was poured into wann aqueous ethanol and allowed to crystallize. The yellow crystals were obtained in a yield 4.0 g. (15.1% M.P. 220. On recrystallization from ethanol, the melting point rose to 227-228".

When the above reaction was carried out in the presence of concentrated hydrochloric acid (10 cc.) instead of triethanolamine (5 cc.), the same product resulted, M.P. 227-228", yield 2.5 g. (9.4%). The infrared spectra of both products were identical.

EXAMPLE VIII Methyliodide and ethyliodide derivatives of Z-cyclohexl-enyl cyclohex-I-enyl thiourea, isomer II Z-cyclohex-l-enyl cyclohex-l-enyl thiourea (5.9, 0.085 mole) and ethyl iodide (11.7 g., 0.038 mole) were heated together for one-half hour; the mixture was cooled and filtered and the solid was crystallized from EtOH, yield 9.2 g. (93%), M.P., 214-215. Analysis calculated for C H N SC H I: C, 45.93; H, 6.38; I, 32.38, S, 8.2: N, 7.3%. Found C, 46.1; H, 7; I, 31.9; S, 8.2%, N, 7.2.

The methyl iodide derivative of isomer II was prepared similarly, M.P. 175. Analysis calculated for C H N S.CH I: C, 44.45; H, 6.08; I, 33.58%. Found: C, 43.9%; H, 6.7; I, 33.8%.

The methyl iodide derivative of N-cyclohexylidene N- cyclohex-l-enyl thiourea was prepared according to the above procedure, M.P. 196. Analysis calculated for C H N S.CH I: C, 44.45; H, 6.08; I, 33.58%. Found: C, 44.04; H, 6.6 1; I, 33.11%.

EXAMPLE IX Action of bromine on C H N S, isomers I and II and other compounds prepared by the procedures of this invention.

TABLE III.-INFRARED ABSORPTION BANDS (cnL- BASE CATALYZED REACTION X i l X Stretching Modes, Other Bands H 3235 3050 (01:1),1585 (0:0 or

C=N), 1546 (NH), 1405, 1365 (0:8 2-Methy1 3250,3145 1595 (0:0) 1560-1580 (C- b8, 1530 (NH), 1400, 1370 3-Metl1yl 3380,3200 3050 (OH), 2700, 1595 (C:

C), 1580-1560 (C=N), 1545-1535 (NH), 1400, 1378, 1370 (C=S). 4-Methyl 3360, 3210, 3140"... 3000 (CH), 1595-1580 (C:

C), and (C=N), 1540 (NH), 1405, 1378, 1368 (0:8).

II NH-C-N= (lycloheptanoneun- 3400, 3200, 3170 3050 (CH), 1585-1560 (C:

o and 0:11 1545 (NI-I), 1400,1355 c=s TABLE IV.INFRARED ABSORPTION BANDS (cmr ACID CATALYZED REACTION X i RNHC-NH S 3 R X Stretching Modes,

H H 3350, 3205 3075, 3060 (C-H), 1690 O:C-C:CH-), 1554 (NH), 1368 (0:8). HQ. 3-Methyl 3350,3250,3160 3000 (CH), 1680 C=CC:CH), 1630 (0:), 1610 (0:0), 1545 (NH) 1415. 1380 (C=S). H. 4-Methyl 3420, 3200 3075, 2970 (OH), 1695 C:C--C:CH), 1565, 1550 (NH), 1365 (C=S). Phenyl H 3400, 3300 3050 (CH), 1672 C:C-C:CH-), 1595 (zgylg) 1510 (NH), 1366 H H(EtI) 3400 3050,3000 (CH), 1685 C=CC:CH). 1550 (NH), 1435, 1372 (0:8). H I-I (tetrabromide) 3400, 3195 1550 (NH), 1305 (0:8).

TABLE V.ULTRAVIOLET ABSORPTION BANDS OF BASE CATALYZED CONDENSATION PRODUCTS FROM THI- OUREA AND CYCLIC KETONES.

X E X AMax eMax.

215 H (Methyl iodide derivative) 364 7, 976 267 5, 160 220 16, 349 Z-Methyl 360 8, 335 299 10,070

215 3Methyl 358 10, 000 298 6,380

215 4-Methyl 354 5, 480 299 3, 830

215 Cycloheptanone derivative 685 6, 127 363 12, 970 295.5 6, 908

1 End absorption.

TABLE VI.-ULTRAVIOLET ABSORPTION BANDS OF ACID The foregoing data establishes the structural relationship of the products prepared by the acid and base catalyzed reactions of this invention.

The compounds of this invention are useful as corrosion inhibitors, as chemical intermediates, as pharmaceuticals and as pesticides. The compounds are also useful as dyes or in the preparation of dyes.

The thiourea compound used in the reaction of this invention may be any compound of the formula wherein R is as previously defined to include hydrogen, any C to C or higher molecular weight hydrocarbon group or substituted hydrocarbon group which is stable under the reaction conditions and which does not interfere with the reaction. Examples of such hydrocarbon groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tbutyl, phenyl, naphthyl, anthryl, phenanthryl, radicals derived from triphenylene and naphthacene, methyl phenyl, ethylphenyl, propylphenyl, butylphenyl, t-butylphenyl, methylnaphthyl, ethylnaphthyl, methylanthryl, the corresponding aralkyl radicals including in addition to those already disclosed, phenylpropyl, naphthylpropyl, naphthylbutyl, and such other cycloaliphatic radicals as cyclopentyl, cyclohexyl and cycloheptyl. Various substituents such as hydroxyl, halo, particularly fiuoro and alkoxy (having 1 to 4 carbon atoms) may be present in R as long as same do not interfere with the reactions.

Species of thiourea compounds include thiourea, methyl thiourea, ethyl thiourea, N-phenyl thiourea, propyl thiourea, N-(O-tolyl) thiourea, N-(M-tolyl) thiourea, N-(P-tolyl) thiourea, and the like. Thiourea compounds not having an --NH group will not work in the reaction.

The cyclic ketoncs used to prepare the products of this invention can be any compound having the structure wherein R is a divalent radical which may consist of unsubstituted methylene chains of 2 to 9 carbon atoms,

ll i.e., (CH where n is 2 to 9, or substituted methylene chains of 2 to 9 carbon atoms containing substituents of the group consisting of methyl, ethyl, propyl, butyl, chloro and fluoro, as previously defined provided no more than one su-bstituent is attached to any methylene group and preferably wherein one beta carbon atom in the formula is unsubstituted.

Examples of R include and similar structures.

The condensation reaction of this invention may be conducted at a temperature of about 150 C. and is preferably carried out at a temperature of about 150 to 200 C. or the reflux temperature of the reaction mixture. Although the mole ratios of reactants is not critical it is preferred that about 1.0 mole of thiourea be reacted with about 2.0 moles of the cyclic ketone. The reactants can be added or mixed in any order.

Any mineral acid or strong organic acid can be used to conduct the acid catalyzed reaction. The mineral acids include, for example and without limitation, the haloacids (HCL, HI, HBr and HF), sulfuric acid (concentrated) nitric acid (dilute), phorsphoric acid (ortho or meta) and boric acid. The organic acids include strong sulfonic acids, halo-organic acids, such as trichloroacetic acid and the like. The acids are used in dilute or concentrated form.

The base catalyzed reaction is conducted at a temperature of about 150 C. to 250 C. and preferably at 150 C. or the reflux temperature of the reaction mixture. Any alkaline material can be used as the catalyst to include both'inorganic and organic bases such as alkali metal hydroxides, sodium, potassium, lithium, and cesium hydroxides, alkaline earth metal hydroxides and oxides such as calcium oxide or hydroxide, barium oxide or hydroxide or the octahydrate, etc. Organic bases include the aliphatic and aromatic amines, i.e., triethanolamine, diethanolamine, propylamine, aniline, methylamine and pyridine. The amount of catalyst used is subject to variation and an excess of catalyst does not appear to interfere with the reaction. An excess of acid catalyst appears to increase the yields. The amount of catalyst used for best results can be determined by experiments. In general about 3 to 8 cc. of an amine such as triethanolamine per mole of the cyclic ketone and about 10 to 50 cc. of concentrated hydrochloric acid per mole of cyclic ketone is used. Adjustments in these amounts of catalyst to accommodate the properties of a particular acid or base are within the skill of the art.

No special precautions are necessary in carrying out either the base or acid catalyzed reaction. The reaction mixture is taken up in a solvent, after a reaction time of l to 10 hours, the solvent being any liquid aliphatic (ethanol, propanol, etc.) alcohol or ketone. Other solvents such as hexane, benzene, toluene, xylene, dioxane, dimethylsulfoxide and the like may be used.

12 The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

I claim: 1. A compound of the formula 8 H is l r R C=N-ONC J wherein R is a substituted or unsubstituted methylene chain of the formula (CH wherein n is 2 to 5, said substituents consisting of up to three members of the group consisting of methyl, ethyl, propyl, butyl, chloro, and fluoro.

2. A compound in accordance with claim 1 in which R is a divalent unsubstituted methylene chain of the formula -(CH wherein n is 2 to 5.

3. A compound in accordance with claim 2 in which n is 4.

4. A compound in accordance with claim 2 in which n is 5.

5. A compound in accordance with claim 1 in which R is a substituted methylene chain of the formula =(CH wherein n is 2 to 5, said substituents consisting of up to three members of the group consisting of methyl, ethyl, propyl, butyl, chloro, and fluoro.

6. A compound in accordance with claim 5 in which Y is methyl.

7. The method of preparing compounds of the formula which comprises reacting about 2 moles of a cyclic ketone of the formula wherein R is a substituted or unsubstituted methylene chain of the formula -(CH wherein n is 2 to 4, said substituents consisting of up to three members of the group consisting of methyl, ethyl, propyl, butyl, chloro, and fluoro, with about 1 mole of a thiourea compound having at least three unsubstituted hydrogen atoms attached to the nitrogen atoms in the presence of a base catalyst.

8. The method in accordance with claim 7 in which said reaction is conducted at a temperature of about C. to 250 C. and the catalyst is triethanolamine.

9. The method in accordance with claim 8 in which said thiourea compound is a member of the group consisting of thiourea, methylthiourea, ethylthiourea, N- phenylthiourea, propylthiourea, N-(o-tolyl) thiourea, N- (m-tolyl) thiourea and N-(p-tolyl)thiourea.

10. The reaction product of the compound of claim 1 with a compound selected from the group consisting of methyl iodide, ethyl iodide, dibromide and tetrabromide.

111. The method of preparing compounds ofthe formu a where comprises reacting about 2 moles of the corresponding cycloheptanoneof the formula wherein R is a substituted or unsubstituted methylene chain of the formula (CH wherein n. is 5, said substituents consisting of up to three members of the 13 group consisting of methyl, ethyl, propyl, butyl, chloro, and fluoro, with about 1 mole of a thiourea compound having at least three unsubstituted hydrogen atoms attached to the nitrogen atoms in the presence of a catalyst selected from the group consisting of an acid and a base.

12. The method in accordance with claim 11 in which said thiourea compound is a member selected from the group consisting of thiourea, methylthiourea, ethylthiourea, N-phenylthiourea, propylthiourea, N-(o-tolyl) thiourea, N-(m-tolyl) thiourea and N-(p-tolyl) thiourea.

13. The method in accordance with claim 11 in which the catalyst is hydrochloric acid. 

1. A COMPOUND OF THE FORMULA 